Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been is applied as hole transport material in organic electronic devices for more than 20 years. However, the redundant sulfonic acid group of PEDOT:PSS has often been overlooked. Herein, PEDOT:PSS‐DA is prepared via a facile doping of PEDOT:PSS with dopamine hydrochloride (DA·HCl) which reacts with the redundant sulfonic acid of PSS. The PEDOT:PSS‐DA film exhibits enhanced work function and conductivity compared to those of PEDOT:PSS. PEDOT:PSS‐DA‐based devices show a power conversion efficiency of 16.55% which is the highest in organic solar cells (OSCs) with (poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)‐4‐fluorothiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithio‐phene))‐co‐(1,3‐di(5‐thiophene‐2‐yl)‐5,7‐bis(2‐ethylhexyl)‐benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione))] (PM6):(2,2′‐((2Z,2′Z)‐((12,13‐bis(2‐ethylhexyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2′′,3′:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2‐g]thieno[2′,3′:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile) (Y6) as the active layer. Furthermore, PEDOT:PSS‐DA also exhibits enhanced performance in three other donor/acceptor systems, exhibiting high compatibility in OSCs. This work demonstrates that doping PEDOT:PSS with various amino derivatives is a potentially efficient strategy to enhance the performance of PEDOT:PSS in organic electronic devices.